Zwitterionic polyamines and process for their production

ABSTRACT

A zwitterionic polyamine comprising a linear or branched hydrophobic polyamine backbone having 2 to 10 tertiary amino nitrogen atoms and a spacer between two tertiary nitrogen atoms wherein the spacer is, for example selected from C 8 -C 16 -alkylene, C 5 -C 15 -cyloalkylene, wherein in formula (IV) R═C 1 - to C 22 -alkyl or C 7 -C 22 -aralkyl and n=3 to 6, at least one tertiary amine end group of the polyamine backbone contains two groups having formula (V) or (VI), wherein A means an ethylene oxide unit, a propylene oxide unit, a unit of butylene oxides and a tetrahydrofuran unit, n is a number of from 1 to 50, X is an anionic group such as —SO 3 M, with the proviso that in formula (VI) one X may also be hydrogen and M is hydrogen, alkai metal or ammonium, or contains one group of formula (V) or (VI) and one group selected from radicals consisting of formula (VII), C 1 - to C 22 -alkyl and C 7 -C 22 -aralkyl the meaning of A and n is the same as in formula (V) or (VI), said zwitterionic polyetherpolyamine having a molecular weight up to 9000 and optionally containing up to 100% of the nitrogen atoms quaternize, and a process for the production of zwitterionic polyamines by alkoxylating said polyamines, introducing anionic groups into the alkoxylated polyamines and optionally quaternizing them before or after the introduction of anionic groups. The zwitterionic polyamines are used in detergents.

This application is a 371 of PCT EP00/06296 filed Jul. 5, 2000.

The present invention relates to zwitterionic polyamines and a processfor their production by alkoxylation of polyamines and introduction ofanionic groups.

BACKGROUND OF THE INVENTION

EP-A-0,111,976 relates to watersoluble zwitterionic compounds havingclay soil removal/anti-redeposition properties. An example of such acompound is a with chlorosulfonic acid sulfated quaternized additionproduct of ethoxylated tetraethylenepentamine with a total degree ofethoxylation of 21.

EP-A-0,112,592 relates to zwitterionic polymers which are for exampleobtained by alkoxylation of polyalkyleneamines such astriethylenetetramine or tetraethylenepentamine or of polyethyleneimines,sulfonation of the alkoxylated products and subsequent quaternization.The zwitterionic products disclosed in the above patents have clay-soilremoval and anti-redeposition properties when used in detergentcompositions, however their effectiveness in dispersing and removingclay embedded in the fabric into the laundry liquor is not sufficient.Furthermore the specifically disclosed compounds of this literaturereference are thermally instable.

GB-A-2,220,215 relates to sulfated alkoxylated mono- or polyaminesderived from polymethlenediamines with 2-6 methylene groups between thenitrogen atoms or polyalkylenepolyamines in which the alkylene contains2-4 carbon atoms and containing 3-6 amino groups. They may bear a longchain-alkyl substituent at one of the nitrogen atoms and arequaternized. However it was found that these polymers are not favorablefor clay soil removal within laundry operations where anionicsurfactants are present.

U.S. Pat. No. 4,739,094 discloses alkoxylated aminopolyethers containingunits of ethylene oxide and propylene oxide and having a molecularweight of from 10,000 to 150,000. The alkoxylated aminopolyethers arewater-soluble and are used in 5 to 60% strength by weight aqueoussolution in the preparation of coal/water slurries. If appropriate, thealkoxylated aminopolyethers can also be reacted with carboxylic acidanhydrides, amidosulfonic acids and urea, acid chlorides of sulfur or ofphosphorus or chloroacetic acid esters. The reaction products can beconverted into ionic compounds by subsequent neutralization orhydrolysis.

It is therefore an object of the invention to provide new polymers withimproved thermal stability.

SUMMARY OF THE INVENTION

The above object is achieved with a zwitterionic polyamine comprising alinear or branched hydrophobic polyamine backbone having 2 to 10tertiary amino nitrogen atoms and a spacer between two tertiary aminonitrogen atoms wherein the spacer is selected from the group consistingof C₃-C₁₅-alkylene, C₅-C₁₅-cycloalkylene

wherein in formula I, II and III

B is C₂-C₁₆-alkylene, C₅-C₁₅-cycloalkylene

D is C₄-C₁₆-alkylene, C₅-C₁₅-cycloalkylene

O is 1 or 2,

p is 3 to 8

wherein in formula IV

R=C₁- to C₂₂-alkyl or C₇-C₂₂-aralkyl and n=3 to 6,

at least one tertiary amine end group of the polyamine backbone containstwo groups having the formula

wherein

A means an ethylene oxide unit, a propylene oxide unit, a unit ofbutylene oxides and a tetrahydrofuran unit,

n is a number of from 1 to 50,

X is —SO₃M, —CH₂—CH₂—SO₃M, —CH₂—CH₂—CH₂—SO₃M,

 with the proviso that in formula VI one X may also be hydrogen and

M is hydrogen, alkali metal or ammonium,

or contains one group of formula V or VI and one group selected fromradicals consisting of

C₁- to C₂₂-alkyl and C₇-C₂₂-aralkyl, the meaning of A and n is the sameas in formula V or VI,

said zwitterionic polyamine having a molecular weight up to 9,000optionally containing up to 100% of the nitrogen atoms quaternized.

The object is also achieved with a process for the production of azwitterionic polyamine which comprises a first step wherein

(i) a linear or branched hydrophobic polyamine having 2to 10 tertiaryamino nitrogen atoms and a spacer between two tertiary amino nitrogenatoms wherein the spacer is selected from the group consisting of

C₈- to C₁₆-alkylene, C₅- to C₁₅-cycloalkylene

wherein in formula I, II and III

B is C₂-C₁₆-alkylene, C₅-C₁₅-cycloalkylene

D is C₄-C₁₆-alkylene, C₅-C₁₅-cycloalkylene

o is 1 or 2,

p is 3 to 8

wherein in formula IV

R=C₁- to C₂₂-alkyl or C₇-C₂₂-aralkyl and n=2 to 6,

is reacted with

(ii) at least one C₂- to C₄-alkylene oxide or tetrahydro furane at sucha ratio that on each NH group of the polyamine 1 to 50 units of thealkylene oxide or of tetrahydrofurane are added,

a second step wherein the alkoxylated polyamine obtained in the firststep is reacted with a compound selected from the group consisting of ahalogen sulfonic acid, halogen phosphorous acid, vinyl sulfonic acid,propane sultone, halogen acetic acid, acrylic acid, methacrylic acid,vinyl phosphorous acid and the alkali metal or ammonium salts of thesaid acids, in such a manner that at least one tertiary amine end groupof the alkoxylated polyamine contains two groups having the formula

wherein

A means an ethylene oxide unit, a propylene oxide unit, a unit ofbutylene oxides and a tetrahydrofuran unit,

n is a number of from 1 to 50,

X is —SO₃M, —CH₂—CH₂—SO₃M, —CH₂—CH₂—CH₂—SO₃M,

 with the proviso that in formula VI one X may also be hydrogen and

M is hydrogen, alkali metal or ammonium,

or contains one group of formula V or VI and one group selected fromradicals consisting of

the meaning of A and n is the same as in formula V or VI,

and optionally

a third step wherein up to 100% of the tertiary nitrogen atoms of thereaction product obtained in the second step are quaternized, saiddegree of quaternization, may also be obtained by first quaternizing thereaction product obtained in the first step and subsequently carryingout the second step.

Preferred zwitterionic polyamines contain two groups of formula V or VIattached to the tertiary nitrogen atoms of the end groups of thepolyamines. Especially preferred zwitterionic polyamines contain thenitrogen atoms of the end groups of the polyamine backbone quaternizedand, as substituents, two groups of formula V or VI and one C₁- toC₂₂-alkyl group or a hydroxyalkyl group. In most cases the nitrogen endgroups of the polyamine backbone are quaternized and contain assubstituents two groups of formula V and a C₁- to C₂₂-alkyl group. Otherpreferred zwitterionic polyamines contain quaternized amino nitrogen endgroups bearing, as substituents, two groups of formula V and ahydroxyethyl or hydroxypropyl group.

The substituent A in formulae V and VI may have the followingstructures:

Other zwitterionic polyamines are charaterized in that the spacerbetween two nitrogen atoms of the polyamine backbone is a cyclic C₅- toC₁₅-alkylene group.

Of particular interest are zwitterionic polyamines wherein the polyaminebackbone between the nitrogen atoms is derived from an amine selectedfrom the group consisting of bis(hexamethylene)triamine,N,N′-bis(3-aminopropyl)piperazine, N,N′-bis(2-aminoethyl)piperazine andbis(3-aminopropyl)hexamethylenediamine and wherein at least one tertiaryamine end group of the polyamine backbone contains two groups havingformula V or VI.

The zwitterionic polyamine is derived from a linear or branchedhydrophobic polyamine. The backbone of the polyamine contains 2 to 10tertiary amino nitrogen atoms and has one spacer between two tertiaryamino nitrogen atoms. Polyamines containing a C₈- to C₁₆-alkylene groupas spacer are for example 1,8-diaminooctane, 1,10-diaminodecane and1,12-diaminododecane. Examples of suitable polyamines containing theabove spacers of formula I-IV are dipropylenetriamine,tripropylenetetramine, bis(hexamethylene)triamine,bis(octamethylene)triamine, aminoethylpropylenediamine,aminoethylbutylenediamine, aminoethylhexamethylenediamine,N,N′-bis(aminoethyl)propylenediamine,N,N′-bis(aminoethyl)butylenediamine,N,N′-bis(aminoethyl)hexamethylenediamine,N,N′-bis(aminopropyl)ethylendiamine,N,N′-bis(aminopropyl)butylenediamine,N,N′-bis(aminopropyl)butylendiamine,N,N′-bis(aminopropyl)hexamethylenediamine,N,N′-bis(aminopropyl)ethylenediamine,N,N′-bis(3-aminopropyl)-N-methylamine,N-(dimethylaminopropyl)propylenediamine,N,N′-dimethyl-1,3-diaminopropane; N,N-bis (3-aminopropyl) -N-octylamineand N,N-bis (3-aminopropyl)-N-ethylamine.

Polyamines with spacers consisting of a cyclic C5- to C15-alkylene groupare for example 1,3-cyclohexylenediamine,4-methyl-1,3-cyclohexylenediamine, 2-methyl-1,3-cyclohexylenediamine,isophoronediamine and 4,4′-diamino(biscyclohexylene)methane.

The zwitterionic polyamines can also be prepared from polyamines whichcontain other cyclic spacers. Such polyamines are, for example, o-, m-,and p-di(aminomethylen)benzene, N,N′-bis(aminoethyl)piperazine,N,N′-bis(aminopropylpiperazine and N-aminopropylpiperazine.

Especially preferred zwitterionic polyamines may be characterized by thefollowing formula

wherein

EO is —CH₂—CH₂—O—

M is H, Na, K or ammonium and

n is 15-25.

The weight average molecular weight Mw of the zwitterionicpolypolyamines is up to 9,000, preferably of from 1,500 to 7,500 andmore preferably of from 2000 to 6,000. The zwitterionic polyamines canbe soluble or dispersible in water and aqueous or non-aqueous solventsor formulations. In one preferred embodiment of the present inventionthey are water-soluble. These water soluble zwitterionicpolyetherpolyamines are used in laundry detergent compositions and havean excellent degree of clay soil removal from fabrics.

The zwitterionic polyamines are net anionic. Preferably the averagenumber of anionic charges resulting from groups X in formulae V and VIexceeds the average number of cationic charges resulting from protonatedor quaternized amine groups by a factor of more than 1.2, more preferredof more than 1.5, most preferred of more than 1.8.

The zwitterionic polyamines of the invention are prepared in amultistage process. In the first step of this process a linear orbranched polyamine having 2 to 10 primary or secondary nitrogen atomsand containing one of the above spacers between two nitrogen atoms isreacted with a least one C₂- to C₄-alkylene oxide or tetrahydrofurane atsuch a ratio that on each NH group of the polyamine 1 to 50, preferably15 to 25 alkylene oxide units or tetrahydrofurane units are added.Ethylene oxide and propylene oxide are the preferred alkoxylatingagents. If a mixture of alkylene oxides is added to the amino nitrogenthen the polymerized alkylene oxides may be present in statisticaldistribution or as blocks. For example one can add first 10 to 20 ofethylene oxide units per NH group in the polyamine and then add 5 to 10propylene oxide units or vice versa.

Most preferred ethylene oxide alone or combinations of 1-15% propyleneoxide or 1-10% butylene oxide with 85-99, 90-99% ethylene oxiderespectively are used. If a combination of ethylene oxide and propyleneoxide or butylene oxide is used preferably the propylene oxide orbutylene oxide is reacted first with the NH groups of the polyamine andthe ethylene oxide is added after that.

The above described procedure gives polyalkoxylated products which havegroups of formula

—(A)_(n)—H,

wherein A and n have the meaning given for formula V.

The linear or branched polyamines are preferably ethoxylated in thefirst step of the production of the zwitterionic polyamines.

In order to produce zwitterionic polyamines having end groups of formulaVI a linear or branched polyamine having 2 to 10 nitrogen atoms andcontaining at least 2 primary or secondary amino nitrogen groups isreacted with up to 1 glycidol per NH group. The reaction product thusobtained is in the first step of the process according to the inventionalkoxylated at the OH groups and remaining NH groups as described above.The reaction of glycidol with said polyamine may be carried out to suchan extent that at least 50 to 100% of the NH groups of the polyamine aresubstituted by one glycidol unit.

In the second step of the production of the zwitterionic polyamines ananionic group is introduced into the alkoxylated polyamines obtained inthe first step. This may be achieved by reacting the alkoxylatedpolyamines in a Michael type addition reaction with acrylic acid,methacrylic acid, vinyl sulfonic acid, vinylphosphonic acid or theiralkalimetal or ammonium salts or by reacting them with halogen sulfonicacid, halogen phosphorous acid, propane sultone or halogen acetic acid.The preferred component for introducing anionic groups is chlorosulfonicacid.

Dependent on the amount of anionic agent used in the second stepzwitterionic products are obtained which contain either two substituentsof formula V or VI or contain only one of them, if, for instance, onlyone mole of the anionic agent is used per one mole of OH end group ofthe alkoxylated polyamine. The non-reacted end groups of the alkoxylatedpolyamine may be characterized by a group selected from radicalsconsisting of

the meaning of A and n is the same as in formula V or VI.

The degree of substitution of the OH groups in the alkoxylatedpolyamines is such, that the finally resulting zwitterionic polyamine isnet anionic at the pH of intended use; e.g. from 40% up to 100% of theOH group a substituted by an anionic group. Preferably more than 60%,more preferred more then 80%, most preferred 90-100% of the OH-groupsare substituted by an anionic group.

Moreover the zwitterionic polyamines may also contain only onesubstituent of formula V or VI and instead of the above describedradicals a C₁-C₂₂-alkyl group or a C₇- to C₂₂-aralkyl group. Suchcompounds result when the polyamine used in the first step containssecondary amino groups having a C₁- to C₂₂-alkyl or a C₇- to C₂₂-aralkylsubstituent.

The zwitterionic polyamines obtained in the second step may optionallyreacted in a third step with a quaternizing agent. Alternatively,quaternized products may also be obtained by first quaternizing thereaction products obtained in the first step, i.e. the polyalkoxylatedpolyamines. Suitable quaternization agents are for example C₁- toC₂₂-alkylhalides, C₇- to C₂₂-aralkyl halides C₁-C₂-dialkylsulfates oralkylene oxides. Examples of quaternizing agents are dimethyl sulfate,diethyl sulfate, methyl chloride, ethyl chloride, methyl bromide, ethylbromide, butyl bromide, hexyl chloride, benzyl chloride, benzyl bromide,ethylene oxide or propylene oxide. Dialkylsulfates, C₁-C₄-alkylchloridesand benzyl chloride are preferred. Dimethyl sulfate is the mostpreferred quaternizing agent. Up to 100% of the tertiary nitrogen atomsof the zwitterionic polyamine may be quaternized. If there is aquaternization step, then the degree of quaternization is, for example,10 to 100%, preferably at least 25% and more preferably 75 to 100%.

According to a preferred embodiment of the process for the production ofzwitterionic polyamines in the first step

(i) a polyamine selected from the group consisting ofbis(hexamethylene)triamine, bis(aminopropyl)piperazine,N,N′-bis(aminopropyl)hexamethylenediamine andN,N,N′,N″,N″-penta(2,3-dihydroxypropyl)-bis(hexamethylene)triamine—thelatter is obtained by reacting bis(hexamethylene)triamine with glycidolin a molar ratio of 1:5)—is reacted with

(ii) an alkylene oxide selected from the group consisting of ethyleneoxide, propylene oxide, butylene oxide and mixtures of the said alkyleneoxides, at such a ratio that on each NH group of the polyamine 15 to 40units of the alkylene oxide are added,

in the second step

the alkoxylated polyamine obtained in the first step is reacted withchlorosulfonic acid in such ratio that at least one teritary end groupof the polyamine contains two groups having the formula

—(A)_(n)—X  (V),

wherein

A is an ethylene oxide unit, a propylene oxide unit or a butylene oxideunit,

n is 15-40 and

X is SO₃H,

and

in the third step

the zwitterionic reaction product of the second step is quaternized withdimethyl sulfate, methyl chloride or benzyl chloride.

The quaternization can also be carried out as a second step in themultistage process for the production of zwitterionic polyamines. Thealkoxylated polyamine obtained in the first step is quaternized up to100% and subsequently reacted with chlorosulfonic acid or another agentcapable to introduce an anionic group. This procedure is preferred forthe production of quaternized zwitterionic polyamines.

The zwitterionic polyamines are used as additive in laundry detergentcompositions which provide enhanced hydrophilic soil, inter alia, clay,removal benefits. The new zwitterionic polyamines are especially usefulin detergents comprising a surfactant system which comprises mid-chainbranched surfactants inter alia mid-chain branched alkyl sulphonates.The zwitterionic polyamines are additionally used as effectivedispersants for hydrophilic particles within aqueous and nonaqueoussolutions and formulations.

The degree of quaternization and of sulfatation was determined by¹H-NMR. The amine number was determined by amine titration according toDIN 16 945.

EXAMPLE 1 (a) Ethoxylation of bis(Hexamethylene)triamine (“BHMT”)

A pressurizable 5 1 autoclave fitted with a stirrer and a heating devicewas the sealed and three times pressurized with nitrogen at 10 bar.150.5 g (0.7 mole) of BHMT and 15 g of water were placed in theautoclave which was heated to 80° C. The autoclave was then sealedpresure-tight and three times pressurized with nitrogen at 5 bar andthereafter the pressure released. The contents of the autoclave wereheated while stirring to 110° C. At this temperature 157.1 g (3.57moles) of ethylene oxide were added continuously while maintaining thetemperature between 110-120° C. and the maximum pressure up to 5 bar.The reaction mixture was stirred until the pressure was constant andthen cooled to about 80° C. The pressure was then released, theautoclave three times pressurized with nitrogen at 5 bar and 9.2 g of a50% strenght by weight sodium hydroxide solution were added.

The autoclave was then sealed and vacuum continuously applied to removethe water. The contents of the reactor were heated for four hours at120° C. and at a pressure of 10 mbar. vacuum was removed with nitrogenand the autoclave heated to 140° C. Between 140 and 150° C. 2,926 g(66.5 moles) of ethylene oxide were continuously introduced into theautoclave while stirring. The maximum pressure was 10 bar. The reactionmixture was stirred until the pressure was constant. The contents of thereactor were then cooled to 80° C. and the reactor three timespressurized with nitrogen at 5 bar. 3,238 g of a reaction product wasobtained which was an ethoxylated BHMT containig 20 ethylene oxide unitsper NH group of bis(hexamethylene)triamine (“BHMT EO20”).

(b) Quaternization of Ethoxylated bis(Hexamethylene)triamine with 20moles of Ethylene Oxide per NH Group in BHMT

Into a weighed, 2000 ml, 3 neck round bottom flask fitted with argoninlet, condenser, addition funnel, thermometer, mechanical stirring andargon outlet (connected to a bubbler) is added 455.0 g of BHMT EO20(0.295 mol N, 98% active, M_(W) 4,626 g/mole) and methylene chloride(1000 g) under argon. The mixture is stirred at room temperature untilthe polymer has dissolved. The mixture is then cooled to 5° C. using anice bath. Dimethyl sulfate (39.5 g, 0.31 mol, 99% , m.w.−126.13) isslowly added using an addition funnel over a period of 15 minutes. Theice bath is removed and the reaction is allowed to rise to roomtemperature. After 48 hrs. the reaction is complete. The obtainedproduct was analyzed by titration of the amine-number and by ¹H-NMRintegration to have more then 90% of the nitrogen atoms quaternized.

(c) Sulfation of Quaternized Ethoxylated bis(Hexamethylene)triamine

Under argon, the reaction mixture from the quaternization step (b) iscooled to 5° C. using an ice bath (0.59 mol OH). Chlorosulfonic acid (72g, 0.61 mol, 99% , mw−116.52) is slowly added using an addition funnel.The temperature of the reaction mixture is not allowed to rise above 10°C. The ice bath is removed and the reaction is allowed to rise to roomtemperature. After 6 hrs. the reaction is complete. The reaction isagain cooled to 5° C. and sodium methoxide (264 g, 1.22 mol, Aldrich,25% in methanol, m.w.−54.02) is slowly added to the rapidly stirredmixture. The temperature of the reaction mixture is not allowed to riseabove 10° C.; The reaction mixture is transferred to a single neck roundbottom flask. Purified water (1300 ml) is added to the reaction mixtureand the methylene chloride, methanol and some water is stripped off on arotary evaporator at 50° C. The clear, light yellow solution istransferred to a bottle for storage. The final product pH is checked andadjusted to ˜9 using 1N NaOH or 1N HCl as needed. The obtained productwas analyzed by ¹H-NMR integration to have more then 90% of the OH-endgroups of the polyethylene oxide chains sulfated.

EXAMPLES 2-5

According to the procedure given in Example 1(a) the following amines

Amine 1: bis(hexamethylene)triamine

Amine 2: bis(aminopropyl)piperazine

Amine 3: N,N′-bis(aminopropyl)hexamethylenediamine

Amine 4:N,N,N′,N″,N″-penta(2,3-dihydroxypropyl)-bis(hexamethylene)triamine whichis the reaction product of 1 mole of bis(hexamethylene)triamine with 5moles of glycidol

were reacted with ethylene oxide in the amounts given in Table 1. Theethoxylated amines were then—with the exception of Example 5—quaternizedfollowing the procedure given in Example 1(b) and subsequently sulfatedaccording to the procedure of Example 1 (c). The amounts ofdimethylsulfate and chlorsulfonic acid were adjusted appropriately. Thedegree of quaternization and sulfation is given in Table 1.

TABLE 1 Moles of EO* added per Amine mole of NH number % Amine groups inof EO addi- quaterni- % sulfa- Example No. amine tion product zationtion 2 1 20 40.6 90 50 3 2 20 62.3 90 90 4 3 20 29.9 90 90 5 4 10 29.2 090 *EO: ethylene oxide

What is claimed is:
 1. A zwitterionic polyamine, comprising: a linear orbranched hydrophobic polyamine backbone having 2 to 10 tertiary aminonitrogen atoms and a spacer between two tertiary nitrogen atoms, whereinthe spacer is selected from the group consisting of C₈-C₁₆-alkylene,C₅-C₁₅-cyloalkylene,

wherein in formulae I, II and III B is C₂-C₁₆-alkylene orC₅-C₁₅-cycloalkylene, D is C₄-C₁₆-alkylene or C₅-C₁₅-cycloalkylene, o is1 or 2, p is 3 to 8, wherein in formula IV R is C₁- to C₂₂-alkyl orC₇-C₂₂-aralkyl, and n is an integer of from 3 to 6, wherein at least onetertiary amine end group of the polyamine backbone contains two groupshaving the following formulae

wherein in formulae V and VI A is an ethylene oxide unit, a propyleneoxide unit, a unit of butylene oxides or a tetrahydrofuran unit, n is anumber of from 1 to 50, X is —SO₃M, —CH₂—CH₂—SO₃M, —CH₂—CH₂—CH₂—SO₃M,

 with the proviso that in formula VI one X may also be hydrogen, and Mis hydrogen, alkali metal or ammonium, or wherein at least one tertiaryamine end group of the polyamine backbone contains a) one group offormulae V or VI and b) one group selected from the group consisting of

C₁- to C₂₂-alkyl and C₇-C₂₂-aralkyl; wherein A and n are the same asdefined in formulae V or VI; wherein said zwitterionic polyamine has aweight average molecular weight of up to 9000 and optionally contains upto 100% of the nitrogen atoms in quaternized form.
 2. The zwitterionicpolyamine as claimed in claim 1, wherein the tertiary nitrogen atoms ofsaid tertiary amine end groups of the polyamine backbone contain, assubstituents, two groups of formula V or VI.
 3. The zwitterionicpolyamine as claimed in claim 1, wherein the nitrogen atoms of saidtertiary amine end groups of the polyamine backbone are quaternized andcontain, as substituents, a) two groups of formula V or VI and b) oneC₁- to C₂₂-alkyl group or a hydroxy-alkyl group.
 4. The zwitterionicpolyamine as claimed in claim 1, wherein the nitrogen atoms of saidtertiary amine end groups of the polyamine backbone are quaternized andcontain, as substituents, a) two groups of formula V and b) a C₁- toC₂₂-alkyl group.
 5. The zwitterionic polyamine as claimed in claim 1,wherein the nitrogen atoms of said tertiary amine end groups of thepolyamine backbone are quaternized and contain, as substituents, a) twogroups of formula V and b) a hydroxyethyl or hydroxypropyl group.
 6. Thezwitterionic polyamine as claimed in claim 1, wherein said spacer ofsaid polyamine backbone is a cyclic C₅-C₁₅-alkylene group.
 7. Thezwitterionic polyamine as claimed in claim 1, wherein the polyaminebackbone is derived from a polyamine selected from the group consistingof bis(hexamethylene)triamine, N,N′-bis(3-aminopropyl)piperazine,N,N′-bis(2-aminoethyl)piperazine and

wherein at least one tertiary amine end group of the polyamine backbonecontains two groups having formula V or VI.
 8. A process for theproduction of a zwitterionic polyamine, comprising: (A) reacting thefollowing (i) with the following (ii): (i) a linear or branchedhydrophobic polyamine having 2 to 10 primary or secondary amino nitrogenatoms and one spacer between two nitrogen atoms, wherein the spacer isselected from the group consisting of C₈- to C₁₅-alkylene, C₅- toC₁₅-cycloalkylene,

wherein in formulae I, II and III B is C₂-C₁₆-alkylene orC₅-C₁₅-cycloalkylene, D is C₄-C₁₆-alkylene or C₅-C₁₅-cycloalkylene, o is1 or 2, p is 3 to 8, wherein in formula IV R is C₁- to C₂₂-alkyl orC₇-C₂₂-aralkyl, and n is an integer of from 3 to 6, and (ii) at leastone C₂- to C₄-alkylene oxide or tetrahydrofuran; to obtain analkoxylated polyamine; wherein (i) and (ii) are reacted at such a ratiothat for each NH group of said polyamine 1 to 50 units of the alkyleneoxide are added, (B) reacting said alkoxylated polyamine with a compoundselected from the group consisting of a halogen sulfonic acid, halogenphosphorous acid, vinyl sulfonic acid, propane sultone, halogen aceticacid, acrylic acid, methacrylic acid, vinyl phosphorous acid, an alkalimetal of a halogen sulfonic acid, an alkali metal of a halogenphosphorous acid, an alkali metal of a vinyl sulfonic acid, an alkalimetal of propane sultone, an alkali metal of a halogen acetic acid, analkali metal of acrylic acid, an alkali metal of methacrylic acid, analkali metal of a vinyl phosphorous acid, an ammonium salt of a halogensulfonic acid, an ammonium salt of a halogen phosphorous acid, anammonium salt of a vinyl sulfonic acid, an ammonium salt of propanesultone, an ammonium salt of a halogen acetic acid, an ammonium salt ofacrylic acid, an ammonium salt of methacrylic acid, an ammonium salt ofa vinyl phosphorous acid, in such a manner that at least one tertiaryamine end group of said alkoxylated polyamine contains two groups havingthe formulae

wherein A is an ethylene oxide unit, a propylene oxide unit, a unit ofbutylene oxides or a tetrahydrofuran unit, n is a number of from 1 to50, X is —SO₃M, —CH₂—CH₂—SO₃M, —CH₂—CH₂—CH₂—SO₃M,

 —CH₂—COOM, —CH₂—CH₂—COOM,  —PO₃M₂ or —CH₂—CH₂—PO₃M₂, with the provisothat in formula VI one X may also be hydrogen, and M is hydrogen, alkalimetal or ammonium, or at least one tertiary amine end group of thealkoxylated polyamine contains a) one group of formulae V or VI and b)one group selected from the group consisting of

 wherein A and n are the same as in formulae V or VI, to obtain areaction product having tertiary nitrogen atoms, and, (C) optionally,quarternizing up to 100% of the tertiary nitrogen atoms of the reactionproduct; or (D) quaternizing said alkoxylated polyamine from step (A)and subsequently carrying out step (B).
 9. The process is claimed inclaim 8, wherein said polyamine (i) is selected from the groupconsisting of bis(hexamethylene)triamine, bis(aminopropyl)piperazine,N,N′-bis(aminopropyl)hexamethylenediamine andN,N,N′,N″,N″-penta(2,3-dihydroxypropyl)-bis(hexamethylene)triamine, andwherein said alkylene oxide (ii) is selected from the group consistingof ethylene oxide, propylene oxide, butylene oxide and mixtures of thesaid alkylene oxides, and wherein a ratio between (i) and (ii) is suchthat for each NH group of the polyamine 15 to 40 units of the alkyleneoxide are added, and wherein in step (B) said alkoxylated polyamine isreacted with chlorosulfonic acid in such ratio that at least oneteritary end group of the polyamine contains two groups having theformula —(A)_(n)—X  (V) wherein A is an ethylene oxide unit, a propyleneoxide unit or a butylene oxide unit, n is a number of from 15-40, and Xis SO₃H, and wherein the reaction product having tertiary nitrogen atomsis quaternized with dimethyl sulfate, methyl chloride or benzylchloride.
 10. The process as claimed in claim 8, wherein saidalkoxylated polyamine is quaternized up to 100% and subsequently reactedwith chlorosulfonic acid.
 11. A detergent, comprising: the zwitterionicpolyamine according to claim
 1. 12. The detergent according to claim 11,further comprising: a mid-chain branched surfactant.
 13. The detergentaccording to claim 12, wherein said a mid-chain branched surfactant is amid-chain branched alkyl sulfonate.
 14. A dispersant, comprising: thezwitterionic polyamine according to claim
 1. 15. A dispersion,comprising: the zwitterionic polyamine according to claim 1; and ahydrophilic particle.
 16. The dispersion according to claim 15, furthercomprising: a water or a nonaqueous solvent.
 17. The zwitterionicpolyamine according to claim 1, which is selected from the groupconsisting of

wherein EO is —CH₂—CH_(2—O—,) M is H, Na, K or ammonium and n is anumber of from 15-25.
 18. The zwitterionic polyamine according to claim1, which is net anionic.